Flame-hydrolytically produced titanium dioxide mixed oxide, method of its production and its use

ABSTRACT

Flame-hydrolytically produced titanium dioxide mixed oxide having a BET surface of 10 to 150 m 2  /g and 1 to 30% by weight aluminum oxide or 1 to 30% by weight silicon dioxide is produced by evaporating aluminum chloride or silicon tetrachloride, transferring the evaporated aluminum chloride or silicon tetrachloride, together with an inert gas, into the mixing chamber of a burner, mixing them with hydrogen, air and gaseous titanium tetrachloride, burning the resulting 4-component mixture in the reaction chamber of the burner, and separating the titanium dioxide mixed oxide from the gaseous reaction products.

The present invention relates to a flame-hydrolytically produced titanium dioxide mixed oxide, a method of its production and its use.

BACKGROUND OF THE INVENTION

It is known that titanium dioxide mixed oxide can be produced hydrolytically in the gaseous phase. Thus, published German Patent Application DE-A 9 52 891 describes a method of producing mixed oxides of aluminum and titanium or of titanium and silicon in which the temperature is maintained in the range between 250° and 650° C.

Published German Patent Application DE-A 29 31 810 (U.S. Pat. No. 4,297,143) describes a flame-hydrolytically produced silicon dioxide--titanium dioxide mixed oxide containing 99.9 to 91.1% by weight silicon dioxide and 0.1 to 9.9% by weight titanium dioxide.

Published German Patent Application DE-A 36 11 449 describes a flame-hydrolytically produced aluminum oxide titanium oxide mixed oxide containing 56% by weight aluminum oxide and 44% by weight titanium dioxide.

SUMMARY OF THE INVENTION

The present invention provides a flame-hydrolytically produced titanium dioxide mixed oxide with a BET surface of 10 to 150 m² /g which contains 1 to 30% by weight aluminum oxide or 1 to 30% by weight silicon dioxide as a component of the mixed oxide.

In a preferred embodiment of the invention, the titanium dioxide mixed oxide can have the following physicochemical properties:

    ______________________________________                                         Al.sub.2 O.sub.3 content                                                                               (% by weight)                                                                  1-30                                                   SiO.sub.2 content       (% by weight)                                                                  1-30                                                   Specific surface        (m.sup.2 /g)                                                                   10-150                                                 Primary (unagglomerated) particle size                                                                 5-100                                                  (nm)                                                                           Stamping density        (g/l)                                                                          50-400                                                 Annealing loss (2 hours at 1,000° C.)                                                           (% by weight)                                                                  0.5-5                                                  Chloride content        (% by weight)                                                                  <1                                                     Rutile content          (%)                                                                            20-90                                                  ______________________________________                                    

The invention also provides a method of producing a flame-hydrolytically produced titanium dioxide mixed oxide in which anhydrous aluminum chloride or silicon tetrachloride is evaporated, transferred together with an inert gas, e.g. nitrogen, into the mixing chamber of a conventional burner, mixed in the burner with hydrogen, air and gaseous titanium tetrachloride in such proportions that the correspondingly composed desired Al₂ O₃ /TiO₂ mixed oxide or SiO₂ /TiO₂ mixed oxide results, the 4-component mixture is burned in a reaction chamber, then the solid titanium oxide mixed oxide is separated from the gaseous reaction products and freed, if necessary, in moist air from adhering hydrogen chloride.

The flame-hydrolytic conversion of the invention can be carried out at temperatures of 1,000 to 3,000° C.

The titanium dioxide mixed oxide of the invention can be used for the production of catalysts, catalytic carriers, photocatalysts, ceramics, automobile paints and cosmetic articles (especially as UV absorbers in sunscreen agents) and as heat stabilizers in silicone rubbers.

The titanium dioxide mixed oxide of the invention advantageously has a rather high temperature resistance of the surface. It is fine, very homogenous, very pure and highly dispersible.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The invention is illustrated by the following examples:

Examples

AlCl₃ and TiCl₄ or SiCl₄ and TiCl₄ are volatilized in two separate evaporators (evaporator temperatures: AlCl₃ 250° C., SiCl₄ 100° C., TiCl₄ 200° C.) and the chloride vapors conducted by means of nitrogen into the mixing chamber of a burner. There, they are mixed with hydrogen and dried air and/or oxygen and burned in a reaction chamber. The reaction products are cooled in the coagulation zone to approximately 110° C. The mixed oxides are subsequently separated with a filter. Adhering chloride is removed by treating the powder with moist air at a temperature between 500° and 700° C.

Tables 1 and 2 list the reaction conditions and the product properties for various mixed oxides.

Temperature resistance of the specific surface

The specific surface of mixed oxides 4 and 9 was determined, by way of example, after calcination at temperatures between 500° and 800° C. The residence time was 4 hours in each instance. Undoped pyrogenic titanium oxide P 25 (BET 50 m² /g) was used as reference material. The results are shown in FIG. 1.

The specific surface of P 25 breaks in sharply after 600° C.

The doping with aluminum oxide yields a material with a distinctly more stable surface (800° C.: 30 m² /g instead of 12 m² /g in the case of P 25).

The addition of silicon dioxide yields a powder whose surface is stable over the tested temperature range.

The novel materials can be used at high temperatures and are therefore especially suitable for the production of catalysts and catalytic carriers.

                                      TABLE 1                                      __________________________________________________________________________     Al.sub.2 O.sub.3 /TiO.sub.2 mixed oxides                                                                Stamping                                                                            Annealing                                                                            Chloride                                      TiCl.sub.4                                                                         AlCl.sub.3                                                                         H.sub.2                                                                           Air                                                                               Al.sub.2 O.sub.3                                                                   BET Density                                                                             loss  content                                    No.                                                                               (g/h)                                                                              (g/h)                                                                              (l/h)                                                                             (l/h)                                                                             (%) (m.sup.2 /g)                                                                       (g/l)                                                                               (%)   (%)                                        __________________________________________________________________________     1   264                                                                                19 236                                                                               1643                                                                              6.1 98  159  1.6   0.06                                       2   236                                                                                50 236                                                                               1643                                                                              16.2                                                                               103 145  1.7   0.15                                       3  1466                                                                               114 448                                                                               1276                                                                              6.6 56  308  1.1   0.10                                       4  1363                                                                               188 448                                                                               1276                                                                              11.2                                                                               47  329  0.7   0.16                                       5  1292                                                                               285 448                                                                               1276                                                                              16.7                                                                               58  272  1.0   0.15                                       __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     SiO.sub.2 /TiO.sub.2 mixed oxides                                                                       Stamping                                                                            Annealing                                                                            Chloride                                      TiCl.sub.4                                                                         SiCl.sub.4                                                                         H.sub.2                                                                           Air                                                                               SiO.sub.2                                                                          BET Density                                                                             loss  content                                    No.                                                                               (g/h)                                                                              (g/h)                                                                              (l/h)                                                                             (l/h)                                                                             (%) (m.sup.2 /g)                                                                       (g/l)                                                                               (%)   (%)                                        __________________________________________________________________________     6   268                                                                                17 236                                                                               1643                                                                              5.0 105 162  1.1   0.02                                       7   231                                                                                54 236                                                                               1643                                                                              16.5                                                                               112 151  0.9   0.02                                       8  1423                                                                               118 448                                                                               1276                                                                              6.5 47  287  1.3   0.13                                       9  1346                                                                               208 448                                                                               1276                                                                              9.5 49  274  1.0   0.09                                       10 1258                                                                               296 448                                                                               1276                                                                              16.5                                                                               48  258  1.2   0.06                                       __________________________________________________________________________

BRIEF DESCRIPTION OF FIGURES OF DRAWING

In the drawings,

FIG. 1 is a graph showing the Temperature Stability of the specific surface; and

FIG. 2 is a schematic view of a burner which can be used to carry out the process of the present invention.

In carrying out the invention in the apparatus shown in FIG. 2, the gas-forming metal chlorides, i.e., titanium tetrachloride and aluminum chloride or silicon tetrachloride, are introduced with an inert gas through the inlets 4 and 5 into the mixing chamber 8. Hydrogen and dried air are preheated and introduced through the inlets 6 and 7 into the mixing chamber 8. The four component mixture is advanced into the combustion chamber 1 of the burner and burned in a flame. In order to sustain the flame, an additional quantity of hydrogen can be supplied through the annular chamber 2 which surrounds the combustion chamber 1. 

What is claimed is:
 1. A flame-hydrolytically produced titanium dioxide mixed oxide having a BET surface of 10 to 150 m² /g which contains 1 to 30% by weight of a member of the group consisting of aluminum oxide and silicon dioxide as a component of the mixed oxide, balance titanium dioxide and unavoidable impurities.
 2. A method of producing the flame-hydrolytically produced titanium dioxide mixed oxide according to claim 1 which comprises evaporating up to 30% by weight anhydrous aluminum chloride or silicon tetrachloride, transferring the evaporated aluminum chloride or silicon tetrachloride, together with an inert gas, into the mixing chamber of a conventional burner, together with hydrogen, air and gaseous titanium tetrachloride in effective amounts appropriate to form Al₂ O₃ /TiO₂ mixed oxide or SiO₂ /TiO₂ mixed oxide, burning the resulting 4-component mixture in a reaction chamber at a temperature between 1,000° and 3,000° C., and separating the solid titanium oxide mixed oxide thereby produced from the gaseous reaction products.
 3. A method as set forth in claim 2 including the step of freeing the solid titanium oxide mixed oxide from adhering hydrogen chloride in moist air. 